CN1106410C - High water absorbency polymer and its preparation - Google Patents
High water absorbency polymer and its preparation Download PDFInfo
- Publication number
- CN1106410C CN1106410C CN98109296A CN98109296A CN1106410C CN 1106410 C CN1106410 C CN 1106410C CN 98109296 A CN98109296 A CN 98109296A CN 98109296 A CN98109296 A CN 98109296A CN 1106410 C CN1106410 C CN 1106410C
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- China
- Prior art keywords
- polymerization
- water
- polymer
- high water
- superabsorbent polymer
- Prior art date
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003297 rubidium Chemical class 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229940057950 sodium laureth sulfate Drugs 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- SXHLENDCVBIJFO-UHFFFAOYSA-M sodium;2-[2-(2-dodecoxyethoxy)ethoxy]ethyl sulfate Chemical compound [Na+].CCCCCCCCCCCCOCCOCCOCCOS([O-])(=O)=O SXHLENDCVBIJFO-UHFFFAOYSA-M 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000005672 tetraenes Chemical class 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/32—Polymerisation in water-in-oil emulsions
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Abstract
使用磷酸盐类表面活性剂，提供大粒径、高松密度、高吸水速度、高凝胶固定性的高吸水性聚合物，并提供稳定地工业制造该高吸水性聚合物的方法。高吸水性聚合物的制造方法，它是在分散剂和水溶性自由基聚合引发剂存在下，将含有水溶性聚合性单体及根据需要含有交联剂的水溶液悬浮在疏水性有机溶剂中，在液滴内使上述水溶性聚合性单体进行聚合，其特征在于，分散剂是以下述通式(I)表示的磷酸酯类表面活性剂，而且在上述疏水性有机溶剂中存在聚合度不同的液滴地逐渐供给上述水溶液。其中R1、R2和n如说明书中所述。
To provide a superabsorbent polymer having a large particle size, high bulk density, high water absorption rate, and high gel fixability using a phosphate-based surfactant, and to provide a method for stably industrially producing the superabsorbent polymer. A method for producing a superabsorbent polymer comprising suspending an aqueous solution containing a water-soluble polymerizable monomer and optionally a crosslinking agent in a hydrophobic organic solvent in the presence of a dispersant and a water-soluble radical polymerization initiator, The above-mentioned water-soluble polymerizable monomer is polymerized in the droplet, and it is characterized in that the dispersant is a phosphate-based surfactant represented by the following general formula (I), and there is a difference in the degree of polymerization in the above-mentioned hydrophobic organic solvent The above-mentioned aqueous solution was gradually supplied in droplets. Wherein R 1 , R 2 and n are as described in the specification.
Description
The invention relates to the novel superabsorbent polymeric particles that makes the water-soluble polymeric monomer polymerization and constitute (below, sometimes be called for short " high water absorbency polymer ") and make this particulate method, in more detail, be about median size with specified range and loose density and size distribution is narrow, absorption speed and water absorbent gel stationarity are good, the method that is suitable for the non-spherical high water absorbency polymer of sanitary material etc. and adopts the above-mentioned high water absorbency polymer of the inverse suspension polymerization manufactured of specified conditions.
In recent years, high water absorbency polymer is not only as sanitary materials such as diaper made of paper and physiological articles, and be used for water-proof material, dewfall prevents industrial fields such as agent, preservation agent, solvent dehydration agent, and greening, agricultural use etc., up to the present, several high water absorbency polymers have been proposed.
As this high water absorbency polymer, known have the hydrolyzate of starch-acrylonitrile graft copolymer, carboxymethyl cellulose crosslinked body, cross linked polyacrylate (salt), vinylformic acid (salt)-vinyl alcohol copolymer, a crosslinked polyethylene oxide etc.
As the method for making high water absorbency polymer from the water-soluble polymeric monomer, except the water-soluble polymeric monomer is suspended, is dispersed in the hydrophobic organic solvent, carry out outside the polymeric inverse suspension polymerization, water solution polymerization process etc. also are known, and characteristics such as the shape of resulting high water absorbency polymer roughly depend on means separately.But just known to the inventor, the absorbent resin for the polymerization that adopts in the past obtains also leaves some room for improvement at aspects such as shape, processibility and water absorbing properties.
For example, when adopting aqueous solution polymerization to make high water absorbency polymer, after polymerization, pulverizing process must be arranged, thereby the distribution of the particle diameter of resulting polymkeric substance is generally also broad.Therefore for the particulate part, need the dust countermeasure usually, need pulverization process more usually for coarse fraction.
In inverse suspension polymerization, carry out polymerization in the hydrophobic organic solvent because the monomeric aqueous solution of water-soluble polymeric is dispersed in, so use dispersion agent usually, but dispersion agent is to the powder characteristics and the service performances such as water absorbing properties and water absorbent gel stationarity of the particle diameter that determines resulting high water absorbency polymer and size distribution etc., and then the stable industrial productivity of high water absorbency polymer is brought great effect.
Because such problem is arranged, so propose various suggestions.These suggestions bring corresponding improvement and solve to some extent, but just known to the inventor, can't think desirable improvement.
For example, up to the present, the occasion that the sorbitan fatty acid esters that uses in inverse suspension polymerization uses as dispersion agent (special public clear 54-30710), resulting high water absorbency polymer, median size is little below 100 μ m, and size distribution is also quite broad, therefore add man-hour as powder, need the dust countermeasure, in addition, on service performances such as absorption speed, gel sets, be easy to generate problem.For this reason, propose to increase the whole bag of tricks of median size.
Method as the median size that increases such high water absorbency polymer, generally be to add thickening material at monomer in mutually to carry out polymeric method (spy opens flat 2-191604), but this method increases the viscosity of monomer phase, thereby polymer beads is adhered mutually, all or part becomes block, therefore consider from industrial production, also be difficult to the good method of saying so.
In addition, be purpose to increase median size, proposed to use the method for the tensio-active agent of various novelties.
As such method, for example, use the method for oil soluble cellulose ester or ether of cellulose (special fair 1-17482 and the clear 57-158210 of Te Kai), though the median size of polymkeric substance increases, but residual dispersion agent fusion when drying, polymkeric substance or aggegation are arranged or, also be difficult to the advantageous method of saying so as if the consideration industrial productivity easily attached to the problem on the wall.
In addition, the occasion that has the MAP (spy opens clear 61-209201) of the straight chained alkyl of 12～24 carbon atoms in use, though obtain the polymkeric substance of big particle diameter, but tensio-active agent is low to the solvability of organic solvent, therefore the tolerable limit of creating conditions that stably obtains polymkeric substance is very narrow, if beyond this condition, just causes block polymerization easily, therefore consider the stably manufactured of industry, this method also is difficult to the advantageous method of saying so.
In addition, in the occasion of using Voranol EP 2001 phosphoric acid salt (spy opens flat 4-36304), tensio-active agent is to the solvability height of organic solvent, though can obtain the polymkeric substance of big particle diameter, because adopt polymerization in batch, so it is very narrow stably to obtain the tolerable limit of creating conditions of polymkeric substance, if beyond this condition, just cause block polymerization easily, therefore consider the stably manufactured of industry, this method also is difficult to the advantageous method of saying so.
In addition, in the occasion of using Voranol EP 2001 phosphoric acid salt (spy opens flat 6-93008), though can make the polymkeric substance of big particle diameter reliably, but dispersion agent is a high-hydrophilic, therefore in polymer polymerizing and during dehydration, adhere to the polymerization tank wall intensely, therefore consider the stably manufactured of industry, this method also is difficult to the advantageous method of saying so.
Like this, no matter high water absorbency polymer in the past is to adopt any method of aqueous solution polymerization or inverse suspension polymerization to obtain, and as mentioned above, is all having problems aspect powder characteristics, service performance and the industrial productivity.
The shape of such high water absorbency polymer when being used for sanitary material such as diaper, produces big influence to the service performance of sanitary material.
For example, when high water absorbency polymer uses as the absorption agent in the cartridge of sanitary materials such as diaper made of paper and sanitary towel, take with the high water absorbency polymer laminate structure be dispersed in formation thing between cotton shape soup compound and be configured on the diaper base material, cover the raw-material method of air permeability thin slice thereon, and with behind high water absorbency polymer and the cotton shape soup compound thorough mixing, be configured on the diaper base material, cover the raw-material method of air permeability thin slice thereon.
Under these circumstances; if use the size distribution that obtains with above-mentioned aqueous solution polymerization wide and have a high water absorbency polymer of the broken shape of acute angle; the particle angle that for example particle diameter is big can puncture the air permeability thin slice and expose particle thus, perhaps is easy to generate the problem that little particle in particle footpath or water absorbent gel move and come off from the gap of cotton shape soup compound.
In addition, the high water absorbency polymer that obtains with the inverse suspension polymerization method, be in the past little median size and spherical occasion, polymkeric substance after the distribution also is very easy to move, come off, and no matter in the big occasion of median size, or the wide occasion of size distribution, the problem that still has the mobile of small particle size polymkeric substance and come off.
As mentioned above, the now general high water absorbency polymer that uses, its size, size distribution, shape are inappropriate, therefore just known to the inventor, may not necessarily fully meet the demands aspect powder characteristics and the service performance.
The present invention addresses the above problem.
Promptly, the manufacture method of high water absorbency polymer of the present invention, be in the presence of dispersion agent and water-soluble radical polymerization initiator, the aqueous solution that will contain the water-soluble polymeric monomer and contain linking agent as required is suspended in the hydrophobic organic solvent, make above-mentioned water-soluble polymeric monomer in drop, carry out the method that high water absorbency polymer is made in polymerization, it is characterized in that, dispersion agent is the phosphoric acid ester tensio-active agent with following general formula (I) expression, and will exist the different drop ground of the polymerization degree to supply with the above-mentioned aqueous solution gradually in above-mentioned hydrophobic organic solvent.
(in the formula, R
1The alkyl or the alkylaryl of 8～30 carbon atoms of expression, R
2Expression OH base or formula-(CH
2CH
2O)
m-OR
1Base.M and n represent 1～30 integer.)
In addition, the feature of high water absorbency polymer of the present invention is, with vinylformic acid and/alkali metal salts of acrylic acids is as monomeric unit, non-spherical particle by the polymkeric substance with crosslinking structure constitutes, median size is 300～1000 μ m, the logstandard deviation value of particle diameter is below 0.35, and loose density is 0.3～0.9g/ml.
According to the present invention, in the occasion that adopts inverse suspension polymerization manufactured high water absorbency polymer, use specific phosphoric acid salt tensio-active agent, and utilize the polymerization of fluid drops method to realize polymerization, therefore can be, make high water absorbency polymer at low cost with the above-mentioned speciality that did not in the past have with open-and-shut operation.Such high water absorbency polymer for example is applicable to diaper made of paper and sanitary towel, soil water-holding agent.
Different according to the high water absorbency polymer that the present invention obtains with the spherical shape polymkeric substance that adopts common inverse suspension polymerization method to obtain, be to keep the primary particle of 5～100 μ m melting and the particle aggregate of incorporate structure, median size is greatly to 300～1000 μ m, and size distribution is narrow, thereby improves absorption speed significantly.And, in polymkeric substance, comprise the micropowder below the 100 μ m that become problems such as dust disaster hardly.
And then, polymkeric substance of the present invention is different with the high water absorbency polymer that utilizes the binding agent granulation, and polymkeric substance centre portions primary particle is melting fully, fully integratedization, so water absorbent gel does not return in the primary particle, improve the stationarity of water absorbent gel significantly, this also is its speciality.
Because the present invention uses above-mentioned specific surfactant to carry out polymerization as dispersion agent, the first, can be with the high water absorbency polymer of polymkeric substance to few big particle diameter of condition manufacturing of adhering to of polymerization tank wall.And the special polymerization of putting down in writing among the flat 6-93008 of opening, compare with the tensio-active agent of putting down in writing among the present invention, because use the sulfonate surfactant of high-hydrophilic, thus in polymerization and in the dehydration polymkeric substance to the fierceness of adhering to of polymerization tank wall, so it is satisfied to say so.
The second, polymkeric substance is few to adhering to of polymerization tank wall, therefore can spread all over the ground variation of wide scope and create conditions.And open the tensio-active agent of putting down in writing among the clear 61-209201 the spy, though obtain the high water absorbency polymer of big particle diameter, but the monomeric amount of the water-soluble polymeric of using during polymerization has the upper limit, if add the above amount of polymers of higher limit, just have and cause block polymeric danger etc., the allowed band of the polymerizing condition of energy safe manufacturing is narrow, so it is satisfied to say so.
Moreover the present invention under the reflux conditions of organic solvent, supplies with the water-soluble polymeric monomer gradually and carries out polymerization (this polymerization is called " dropping liquid polymerization " toward contact), therefore can securely and effectively implement.The technology of putting down in writing among the Te Kaiping 4-36304, employing makes the water-soluble polymeric monomer mix in batches in the organic solvent under the cold condition, aggregation container is heated up carry out polymerization (this polymerization is called " polymerization in batch " toward contact), in order to obtain the big polymkeric substance of median size safely, under a spot of monomer condition, must carry out polymerization with high mixing speed, therefore carry out the effective means of also may not necessarily saying so on the industrial production effectively.
The water-soluble polymeric monomer
The water-soluble polymeric monomer of Shi Yonging in the present invention, basically be the water-soluble polymeric monomer that when utilizing this inverse suspension polymerization method to obtain high water absorbency polymer, uses, if be dissolved in water, can use any water-soluble polymeric monomer that conforms with purpose.As preferred water-soluble polymeric monomer, can enumerate (1) ionic monomer, for example (methyl) vinylformic acid and an alkali metal salt thereof, ammonium salt, 2-acrylamide-2-metilsulfate and/or its an alkali metal salt etc., (2) non-ionic monomer, for example (methyl) acrylamide, N, N-DMAA, (methyl) vinylformic acid (2-hydroxyethyl) ester, N-methylol (methyl) acrylamide etc., (3) contain amino polymerizable monomer and quaternary ammonium salt thereof, for example (methyl) vinylformic acid (diethyllaminoethyl) ester, (methyl) vinylformic acid (dimethylamino-propyl) ester etc.The present invention can use one or two or more kinds that select from these groups.At this, the term that is called " (methyl) propylene " also is meant any of " propylene " and " methacrylic ".
Among them, good especially enumerating (methyl) vinylformic acid and/or an alkali metal salt, ammonium salt, (methyl) acrylamide etc.As an alkali metal salt, can enumerate sodium salt, sylvite, lithium salts, rubidium salt etc.But consider from aspects such as resulting polymer properties, easy industrial purchase, securities, preferably sodium salt or sylvite.
Monomer concentration in the monomeric aqueous solution of these water-soluble polymeric generally is more than the 20 weight %～saturation concentration, preferably 25 weight %～saturation concentrations.In addition, (methyl) vinylformic acid, 2-Methacrylamide-2-sulfonate etc. use it more, and part or all is by alkali metal compound and ammonium compound neutral form, be the form of salt, the neutralization ratio (being called degree of neutralization) of this moment is 20～100mol%, 30～100mol% preferably normally.
Linking agent
Above-mentioned water-soluble polymeric monomer, especially acrylic monomer even do not use any linking agent also to produce to a certain degree self-crosslinking, becomes high water absorbency polymer, but in order well balancedly to keep all performances of suction, be preferably in adding in the monomer solution linking agent composition.As the linking agent that uses among the present invention, can enumerate linking agent with 2 above polymerizability unsaturated groups and/or reactive functional group.
That is to say, the words that crosslinking structure is roughly distinguished, can be divided into the method that imports by the monomeric compound copolymerization that makes the polymerizability unsaturated group that has more than 2, and have more than 2 can with polymerization before or the functional group of water-soluble monomer after the polymerization functional group of carboxyl reaction for example, carry out two functional groups reaction and the method that forms as the compound of glycidyl.The latter, if containing this functional group's monomer reacts with the compound that contains this functional group before polymerization, just generate the monomeric compound with 2 above polymerizability unsaturated groups before polymerization, just equal this monomeric compound generation copolymerization yet, we can say with the former does not have in essence variation.Therefore, the present invention there is no need strictness and distinguishes both.
Linking agent with 2 above polymerizability unsaturated groups, can enumerate two or three (methyl) esters of acrylic acid of (1) polyvalent alcohol, polyvalent alcohol for example, be ethylene glycol, propylene glycol, TriMethylolPropane(TMP), glycerol, polyoxyethylene glycol, polyoxypropylene diols, Polyglycerine etc., (2) in above-mentioned (1), unsaturated acid, except (methyl) vinylformic acid, it for example is toxilic acid, acid such as fumaric acid, (3) bisacrylamide class, for example be N, N-methylene bisacrylamide etc., (4) epoxide reacts two or three (methyl) esters of acrylic acid that obtains with (methyl) vinylformic acid, (5) polymeric polyisocyanate reacts two (methyl) acrylic-amino carbamoyl ester class that obtains with (methyl) crylic acid hydroxy ester, for example polymeric polyisocyanate is the toluylene group diisocyanate, hexamethylene diisocyanate etc., (6) polynary allyl group, for example allylation starch, the allylation Mierocrystalline cellulose, Phthalic acid, diallyl ester, tetraene propoxy-ethane, tetrahydroxybutane three allyl ethers, the trimethylolpropane tris allyl ether, glycol ether two propylene ethers, trimellitic acid triallyl etc.Among them, for purposes of the invention, preferably ethylene glycol bisthioglycolate (methyl) acrylate, propylene glycol (methyl) acrylate, polypropylene glycol two (methyl) acrylate, N, N-methylene-bis (methyl) acrylamide etc.
As the original monomeric functional group from high water absorbency polymer, for example having more than 2 carboxyl is the linking agent of reactive base, for example can enumerate 2-glycidyl ether compound, halogen epoxide, isocyanate compound etc.Among them, be good especially with the 2-glycidyl ether compound.As the object lesson of 2-glycidyl ether compound, can enumerate ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, interior glycol diglycidylether, polypropylene glycol diglycidyl ether, glycerol diglycidylether, polyglycerol diglycidylether etc.Among them, be good with ethylene glycol diglycidylether.In addition, in the linking agent that can use, as halogen epoxide, can enumerate Epicholorohydrin, Beta-methyl Epicholorohydrin etc., but, can enumerate 2,4-toluylene group diisocyanate, hexamethylene diisocyanate etc. in the present invention as isocyanate compound.These linking agents are in the high-hydroscopicity monomer that is generated by typical starting monomer polymerization, react afterwards and form crosslinking structure, but as mentioned above, in the object monomer, react in advance, also can be used as linking agent and use with 2 above polymerizability unsaturated groups.
The usage quantity of above-described linking agent, with respect to the water-soluble polymeric monomer, normally 0～10 weight %, preferably 0～5 weight %.
Water-soluble radical polymerization initiator
The polymerization starter that uses among the present invention is a water-soluble radical polymerization initiator.Can enumerate (1) hydrogen peroxide as its example, (2) persulphate, for example Potassium Persulphate, Sodium Persulfate, overcurrent acid ammonium etc., (3) azo-initiator, for example 2, two (2-amidine propane) dihydrochlorides, 2 of 2-azo, two (the N of 2-azo, N-dimethylene isobutyl-amidino groups) dihydrochloride, 2,2-azo two { 2-methyl-N-(1, two (the methylol)-2-hydroxyethyls of 1-) propionic acid amides } etc.These water-soluble radical polymerization initiators can use separately or mix in each group or between each group and use.In addition, hydrogen peroxide or persulphate for example also can be with combinations such as reducing substances such as sulphite, L-xitix and amine salt, use as the initiator of reducto oxydative system.The usage quantity of these polymerization starters, with respect to the water-soluble polymeric monomer, usually with 0.001～5 weight %, it is suitable preferably using with the scope of 0.01～1 weight %.
Hydrophobic organic solvent
The hydrophobic organic solvent that uses among the present invention, if be insoluble in water basically, be inert in polymerization, no matter be any can use.As preferred object lesson, for example can enumerate (1) aliphatic hydrocarbon, for example Skellysolve A, normal hexane, normal heptane, octane etc., (2) clicyclic hydrocarbon, for example hexanaphthene, methylcyclohexane etc., (3) aromatic hydrocarbons, for example benzene,toluene,xylene etc.The stability of buying from industry, quality etc. can be enumerated normal hexane, Skellysolve A, hexanaphthene etc. as best solvent.
The usage quantity of these hydrophobic organic solvents with respect to the monomeric aqueous solution of water-soluble polymeric, adopts 0.5～10 weight % usually, best 0.5～3 weight %.
Dispersion agent
Dispersion agent in the present invention promptly is dispersed in the auxiliary agent in the hydrophobic organic solvent with monomer solution as drop and the phosphoric acid ester tensio-active agent that uses, is the tensio-active agent with general formula (I) expression.These phosphoric acid ester tensio-active agents, all being similar to natural phospholipid (Yelkin TTS, kephalin etc.) on the chemical structure or on physiology, therefore comparing with other tensio-active agents, also is hypotoxicity, low irritant, from the viewpoint of security, be best tensio-active agent.
(in the formula, R
1The alkyl or the alkylaryl of 8～30 carbon atoms of expression, R
2Expression OH base or formula-(CH
2CH
2O)
m-OR
1Base.M and n represent 1～30 integer.)
R
1The preferably alkyl of 8～23 carbon atoms or an alkyl phenyl (that is, being the alkyl of 2～17 carbon atoms).Especially with the former alkyl the best.M and n preferably are respectively 1～20.In this phosphoric acid ester is the occasion of diester, R
2Preferably and comprise above-mentioned R
1The identical R of Soxylat A 25-7
1O-(CH
2CH
2O)
n-.
The usage quantity of these dispersion agents, different and different with monomeric species that uses and other operational condition, but in general, with respect to hydrophobic organic solvent, normally 0.01～5 weight %, the preferably amount of 0.05～2 weight % scope.If addition less than 0.01 weight %, then can not get the dispersion effect as purpose, and surpass 5.0 weight %, when the polymkeric substance after polymerization carried out drying, polymkeric substance was in the agglutinative tendency, all was not satisfied therefore.
Example as representative and preferred phosphoric acid ester has polyoxyethylene nonylplenyl ether phosphoric acid, polyoxyethylene octyl phenyl ether phosphoric acid, polyoxyethylene tridecyl ether phosphoric acid, polyoxyethylene lauryl ether phosphoric acid, polyoxyethylene dinonyl phenyl ether phosphoric acid, polyoxyethylene-De バ ノ Le 25-phosphoric acid, polyoxyethylene-2-second hexyl ether phosphoric acid, polyoxyethylene toluylene phenyl ether phosphoric acid, polyoxyethylene octadecyl ether phosphoric acid, polyoxyethylene octadecyl phenyl ether phosphoric acid, polyoxyethylene eight lauryl ether phosphoric acids, polyoxyethylene dodecylphenyl ether phosphoric acid etc.
They can have been bought as the mixture of phosphoric acid one ester and phosphodiester usually, but the weight ratio of mixture of one ester/diester only otherwise the overslaugh reaction, can use with ratio arbitrarily.
Polymerization/polymkeric substance
The present invention is in the presence of dispersion agent and water-soluble radical polymerization initiator, the aqueous solution that will contain the water-soluble polymeric monomer and contain linking agent as required is suspended in the hydrophobic organic solvent, make above-mentioned water-soluble polymeric monomer in drop, carry out polymerization, make the method for high water absorbency polymer thus, dispersion agent is the phosphoric acid ester tensio-active agent with above-mentioned general formula (I) expression, and will exist the different drop ground of the polymerization degree to supply with the above-mentioned aqueous solution gradually to reaction system in above-mentioned hydrophobic organic solvent.Preferably, supply with the monomeric aqueous solution of water-soluble polymeric in the above-mentioned hydrophobic organic solvent under reflux conditions gradually, carry out inverse suspension polymerization along with the monomeric polymeric of this water-soluble polymeric carries out.
Supply with the monomeric concrete grammar of water-soluble polymeric gradually to polymerization reaction system, 1. following～method shown in 4. etc. is for example arranged.
1. on one side continuously with the monomeric aqueous solution dropping liquid of water-soluble polymeric in hydrophobic organic solvent, carry out polymeric method (continuous dropping liquid polymerization) on one side gradually.
2. on one side intermittently with the monomeric aqueous solution dropping liquid of water-soluble polymeric in hydrophobic organic solvent, carry out polymeric method (intermittently dropping liquid polymerization) on one side gradually.
3. the monomeric aqueous solution of water-soluble polymeric is mixed with a part of hydrophobic organic solvent in advance or disperse and the mixing that obtains/dispersion soln on one side dropping liquid in hydrophobic organic solvent, Yi Bian carry out polymeric method (preceding dispersion method).
4. use 1. above-mentioned～3. method simultaneously.
Moreover the addition means of above-mentioned water-soluble radical polymerization initiator has no particular limits, and preferably adds in advance in the aqueous solution of above-mentioned polymerizability water-soluble monomer.
Polymerization temperature in the above-mentioned polymerization, normally 40～150 ℃, 60～90 ℃ scope preferably, the temperature that above-mentioned hydrophobic organic solvent refluxes is suitable.When this temperature was too high, crosslinking degree extremely improved, so the water-absorbent of polymkeric substance is low, and crossed when hanging down, and not only polymerization velocity is extremely low, and because of induction units needs significantly lengthening, causes the polymerization of burst, and the tendency of easy generation block is arranged.
If the monomeric aqueous solution of water-soluble polymeric is mixed in batches, with polymeric then in batch polymerization carry out above-mentioned inverse suspension polymerization, then obtain as the scope of creating conditions of the water-absorbing polymer of the median size of purpose narrow, with dropping liquid polymerization the same terms under polymerization in, be not easy to remove the heating that produces by polymerization, the situation that generates bulk polymer is arranged.
When above-mentioned inverse suspension polymerization, there is the method for above-mentioned phosphoric acid ester tensio-active agent as dispersion agent, can enumerate the method shown in following (1)～(3).
(1) method of scatter table surface-active agent in hydrophobic organic solvent in advance.
(2) add the method for tensio-active agent at leisure while carrying out above-mentioned polymerization.
(3) use the method for (1)～(2) simultaneously.
Manufacture method according to picture high water absorbency polymer of the present invention, can access median size and be 300～1000 μ m, 300～800 μ m preferably, loose density is 0.3～0.9g/ml, 0.4～0.7g/ml preferably, and the logstandard deviation value (A) of particle diameter is below 0.35, the non-spherical high water absorbency polymer below 0.30 preferably.
The shape of resulting non-spherical high water absorbency polymer, certainly the mixing speed the when kind by changing employed dispersion agent, polymerization, polymerization starter amount etc. change arbitrarily.The representational shape of the high water absorbency polymer that generates is as Fig. 1～shown in Figure 3.The primary particle of 5～100 μ m shown in Figure 1 keeps the botryoidalis polymkeric substance of the low bulk of mutual granulation shape.Shown in Figure 3 is the grain of rice shaped polymer of high bulk density, can't see the existence of primary particle from outward appearance.Fig. 2 illustrates its intermediary rock-like polymkeric substance of picture.No matter obtain the polymkeric substance of which kind of shape of Fig. 1～Fig. 3, its size distribution all is very narrow.For example, on logarithmic probability paper, mark and draw the occasion of size distribution, the value of logstandard deviation (A) that becomes its distributing homogeneity index of expression is below 0.35, preferably below 0.30, said previous methods obtains having the polymkeric substance of not thinking narrow size distribution.
In the present invention, use to have the phosphoric acid based surfactant of ad hoc structure, according to making above-mentioned polymkeric substance, to contain phosphorus atom as a feature at polymer surfaces and inside.Phosphorus content in the polymkeric substance is different because of the kind and the amount of employed tensio-active agent, but with respect to the exsiccant polymkeric substance, and normally 0.001～1%, 0.01～0.1% scope preferably.
In general, lipophilicity such as sorbitan ester and sucrose ester and nonionic surfactant are used for the inverse suspension polymerization of water-soluble monomer, can stably make the globular polymkeric substance, are known.
In the present invention, so-called can stably make non-spherical and polymkeric substance that median size is big, be that the small-particle of 5～100 μ m does not connect and melting fully, integrated, become granular powder, almost can't see the polymkeric substance of spherical shape separately, and can't see the particle new aggegation each other of polymerization end of a period etc. during thinking from polymerization end of a period back to the dehydration end of a period, above-mentioned phosphoric acid ester tensio-active agent drips polymkeric substance with the low polymerization degree at polymerization initial stage with respect to monomer dispersion liquid, make its instability, keep the agglutinative action, on the contrary, think on the contrary with respect to the polymkeric substance second particle after the aggegation limit polymerization of limit and can not finish 2 different functions that are called decentralized stabilization simultaneously.But technical scope of the present invention is not limited to these.
According to the above high water absorbency polymer of the present invention, can be after polymerization directly or utilize decantation and centrifugation to remove the back of desolvating, use means such as drying under reduced pressure machine to carry out drying, obtain as goods.And resulting granules also can form desirable particle diameter by implementing pulverizing, granulation processing etc. as required.
Following embodiment and comparative example are in order to illustrate in greater detail the present invention.Therefore much less the present invention is not limited.
Moreover the test method of carrying out in embodiment and the comparative example is as follows.
(1) water-absorbent
Accurately the about 0.5g water-absorbing polymer of weighing is put into 250 purpose polyamide fibre bags (size of 20cm * 10cm), and dipping is 30 minutes in the artificial urine of 500cc.Then this polyamide fibre bag is picked up, after carrying out removing moisture in 15 minutes, measure its weight, carry out blank revisal, calculate water-absorbent according to following formula.
Water absorbent rate (g/g)=(liquid sucting copolymer weight-blank weight)
÷ water-absorbing polymer weight
Artificial urine composed as follows:
Urea 1.94%
Sodium-chlor 0.80%
Calcium chloride 0.06%
Sal epsom 0.11%
Pure water 97.09%
(2) absorption speed
Use the device of Fig. 4 to measure.On the non-woven fabrics that has on the supporting plate of aperture, place the 1.0g high water absorbency polymer.From following and 0.9% contact with normal saline the time, measure the water regain that high water absorbency polymer absorbs 0.9% physiological saline.The amount that keeps 0.9% physiological saline that absorbed water back 20 minutes of beginning is as absorption speed.
(3) median size and size distribution
With ASTM formula standard sieve from top to bottom according to 8 orders, 12 orders, 20 orders, 24 orders, 32 orders, 40 orders, 60 orders, 80 orders, 100 orders, 120 orders, made up by the order of ware, on uppermost sieve, place about 50g water-absorbing polymer, with the automatic vibrator vibration of Luo Taipushi 1 minute.On logarithmic probability paper, mark and draw retained percentage R, with the particle diameter that is equivalent to R=50% as median size.
Size distribution is used the logstandard deviation value A (reference: " powder technology basis " powder technology basis is compiled the council and compiled, Nikkan Kogyo Shimbun's periodical) that represents with following formula as its index.At this, the value of A is more little, means that size distribution is narrow more.
A＝〔ln(×2/×1)〕×0.5
(the * 1st, the particle diameter during R=84.1%, the * 2nd, the particle diameter during R=15.9%)
(4) loose density
Carry out according to JISK-6721.Carry out 3 times and measure, with mean value as numerical value.
(5) water absorbent gel stationarity
At sheet soup compound (Off ラ Star Off パ Le プ) (adhesion amount: 150g/m
2, scatter the 2.5g water-absorbing polymer equably on the size 19 * 7.5cm).The sheet soup compound of overlapping same size, identical adhesion amount is made easy absorbent pad on the complex body of this water-absorbing polymer/sheet soup compound.At room temperature, use the oil pressure extrusion machine that this absorbent pad is carried out 100Kg load, compression in 20 minutes after, 0.9% physiological saline of 125g is absorbed water by absorbent pad.
On this absorption pad, place 3.5Kg weight made of iron again, use the omnipotent screen(ing) machine (containing flourish hall (strain) system in the well, model MS-1) that swings, the absorbent pad along continuous straight runs is carried out (vibration number: 100 times/minute) vibration in 3 minutes.
Remove load, reclaim the gel that is present in the soup compound respectively and arrive soup compound gel outward because of vibration, measure its weight after, according to following formula calculated for gel stationarity.
Gel sets (%)
=(gel (g) in the soup compound) ÷ (gel (g) that soup compound is outer
Gel (g) in+soup compound) * 100
(6) phosphorus content
Make high water absorbency polymer decompose wet type and decompose, utilize ICP spectrum analysis (induction bonded high frequency plasma spectrum analysis) to measure phosphorus content.
Mensuration is to use セ イ コ-electronic industry (strain) system, SPS1100, and the mensuration wavelength is 203.618nm.
Decomposing wet type decomposes
Weighing 2g high water absorbency polymer in the Ji Yedashi Kjeldahl flask adds 10ml sulfuric acid and 3ml nitric acid, decomposes on electricradiator.
In decomposing test portion, add ion exchanged water, form 50ml, as the mensuration aqueous solution.
Embodiment 1
With 13.5g water dilution 207.7g vinylformic acid, while cool off with among the aqueous sodium hydroxide solution 346.2g of 25 weight % and after, add 0.863g over cure potassium, make its dissolving formation homogeneous solution, be modulated into monomers/initiator solution.
In addition, in 4 mouthfuls of round-bottomed flasks of 3 liters of the volumes that stirrer, reflux cooler, thermometer and nitrogen ingress pipe are housed, put into the 624g hexanaphthene, to wherein adding polyoxyethylene tridecyl ether phosphate (first industrial pharmacy (strain) system of 1.56g as dispersion agent, " プ ラ イ サ-Off A212C "), stirring (500rpm) disperses, flask is carried out being warming up to 75 ℃ behind the nitrogen replacement, hexanaphthene is refluxed.To wherein adding above-mentioned monomers/initiator solution through 46 minutes, after dropping liquid is over, kept 30 minutes at 75 ℃, and then heating, to dewatering to 7% by polymkeric substance with the generation of hexanaphthene azeotropic.
After dehydration ended, one stopped to stir, and polymer beads just is deposited on drag, thereby utilizes decantation separation of polymeric composition granule easily.At the polymkeric substance of 90 ℃ of heating and separating, remove hexanaphthene and some water of attachment removal.Resulting dry polymer is the botryoidalis powder with structure that the primary particle of 5～50 μ m melting mutually.Dry polymer weight is 255g, is about 40g attached to the amount of polymers on flask walls and the stirrer.
Embodiment 2
In embodiment 1, (the first industrial pharmacy system, " プ ラ イ サ-Off A207H ") as dispersion agent, in addition, obtains the botryoidalis powder with same operation with identical gimmick with polyoxyethylene dinonyl phenyl ether phosphoric acid salt.Dry polymer weight is 271g, is about 22g attached to the amount of polymers on flask walls and the stirrer.
Embodiment 3
In embodiment 1, (the first industrial pharmacy system, " プ ラ イ サ-Off A210G ") as dispersion agent, in addition, obtains the rock-like powder with same operation with identical gimmick with polyoxyethylene octyl phenyl ether phosphoric acid salt.Dry polymer weight is 275g, is about 13g attached to the amount of polymers on flask walls and the stirrer.
Embodiment 4
In embodiment 3, make the amount of Potassium Persulphate reach 0.218g, in addition, obtain the rock-like powder with identical gimmick with same operation.Dry polymer weight is 265g, is about 21g attached to the amount of polymers on flask walls and the stirrer.
Embodiment 5
In embodiment 4, make the polymerization revolution reach 300r/min, in addition, obtain grain of rice shape powder with same operation and identical gimmick.Dry polymer weight is 260g, is about 28g attached to the amount of polymers on flask walls and the stirrer.
Embodiment 6
In embodiment 1, (the first industrial pharmacy system, " プ ラ イ サ-Off A208S ") as dispersion agent, in addition, obtains the botryoidalis powder with same operation with identical gimmick with polyoxyethylene-De バ ノ-Le 25-phosphoric acid salt.Dry polymer weight is 257g, is about 27g attached to the amount of polymers on flask walls and the stirrer.
Embodiment 7
In embodiment 1, (the first industrial pharmacy system, " プ ラ イ サ-Off AL ") as dispersion agent, in addition, obtains the botryoidalis powder with same operation with identical gimmick with polyoxyethylene toluylene phenyl ether phosphoric acid salt.Dry polymer weight is 260g, is about 22g attached to the amount of polymers on flask walls and the stirrer.
Embodiment 8
In embodiment 1, in monomer, add the 0.117g ethylene glycol diglycidylether as linking agent, in addition, obtain the botryoidalis powder with identical gimmick with same operation.Dry polymer weight is 250g, is about 53g attached to the amount of polymers on flask walls and the stirrer.
Embodiment 9
In embodiment 6, make the Potassium Persulphate amount reach 0.218g, in addition, obtain the botryoidalis powder with identical gimmick with same operation.Dry polymer weight is 245g, is about 52g attached to the amount of polymers on flask walls and the stirrer.
Comparative example 1
Using the spy to open the dispersion agent of putting down in writing among the clear 61-209201 experimentizes.That is, as the dispersion agent among the embodiment 1, in addition, carry out polymerization with identical gimmick with same operation with a lauryl phosphoric acid.Attached on the wall, when the polymkeric substance dropping liquid begins back about 30 minutes, polymkeric substance is wound on the stirrer, becomes breakneck state from the polymerization initial stage to polymkeric substance, therefore ends converging operation.The polymkeric substance adhesion amount is more than the 500g.
Comparative example 2
Using the spy to open the dispersion agent of putting down in writing among the flat 6-93008 experimentizes.Promptly, in embodiment 1, with sodium laureth sulfate (daylight ケ ミ カ Le ズ (strain) system, " ニ Star コ-Le SBL-2N-27 ", effective constituent 27%) as dispersion agent, addition reaches 5.78g (effective constituent amount 1.56g), in addition, obtains the particulate state powder with same operation with identical gimmick.Extremely adhere in flask walls after 20 minutes from the polymkeric substance dropping liquid, adhesion amount further increases in dehydration.Dry polymer weight is 176g, is about 119g attached to the amount of polymers on flask walls and the stirrer.
Comparative example 3
In embodiment 1, as dispersion agent, in addition, obtain the spherical shape powder with identical gimmick with same operation with the sorbitan monostearate.Dry polymer weight is 235g, is about 60g attached to the amount of polymers on flask walls and the stirrer.
Comparative example 4
In embodiment 1, as dispersion agent, in addition, obtain the spherical shape powder with identical gimmick with same operation with Natvosol.Dry polymer weight is 200g, is about 100g attached to the amount of polymers on flask walls and the stirrer.
Comparative example 5
Use experimental installation and the reagent identical, open the method for putting down in writing among the clear 61-157513 according to the spy and carry out polymerization in batch with embodiment 1.
Promptly, in 4 mouthfuls of round-bottomed flasks of 3 liters of the volumes that stirrer, reflux cooler, thermometer and nitrogen ingress pipe are housed, put into the 624g hexanaphthene, to wherein adding polyoxyethylene tridecyl ether phosphate (first industrial pharmacy (strain) system of 1.56g as dispersion agent, " プ ラ イ サ-Off A212C "), stir (500r/min) and disperse, disperse, flask is carried out nitrogen replacement at 20 ℃.Concurrently in other containers with 13.5g water dilution 207.7g vinylformic acid, while cool off with among the aqueous sodium hydroxide solution 346.2g of 25 weight % and after, add 0.863g over cure potassium, make its dissolving formation homogeneous solution, make monomer/dispersant solution.
From reactor top this monomer/dispersant solution is dropped into hexanaphthene/dispersant solution, stir after 15 minutes, begin to heat up with 70 ℃/h of heat-up rate.The polymerization that begins to happen suddenly when reactor temperature reaches 60 ℃, polymkeric substance become the precarious position that is wound on the stirring rod, therefore end converging operation.The polymkeric substance adhesion amount is more than the 500g.
The measurement result of the median size of above-mentioned polymkeric substance, micro mist amount, size distribution, loose density, phosphorus content, water-absorbent, absorption speed and gel sets is as shown in table 1.
Table 1
Shown in above embodiment 1～9 and comparative example 1～5 (table 1), the present invention uses specific phosphoric acid salt dispersion agent, and adopts the dropping liquid polymerization to carry out polymerization, can be safely and easily implement the few polymerization of polymkeric substance adhesion amount.
| Adhesion amount (g) | Median size (μ m) | Micro mist amount 80 orders following (%) | Size distribution A | Loose density (g/ml) | Phosphorus content ppm | Artificial urine water-absorbent (g/g polymkeric substance) | Absorption speed (g/g polymkeric substance) | Gel sets (%) | |
| Embodiment 1 | 40 | 330 | 1 | 0.26 | 0.57 | 28 | 38 | 23 | 72 |
| Embodiment 2 | 22 | 625 | 0 | 0.3 | 0.52 | 22 | 37 | 25 | 72 |
| Embodiment 3 | 13 | 935 | 0 | 0.3 | 0.41 | 25 | 38 | 26 | 82 |
| Embodiment 4 | 21 | 790 | 0 | 0.34 | 0.79 | 23 | 39 | 18 | 70 |
| Embodiment 5 | 28 | 620 | 0 | 0.31 | 0.68 | 26 | 39 | 21 | 67 |
| Embodiment 6 | 27 | 735 | 0 | 0.34 | 0.47 | 28 | 38 | 23 | 77 |
| Embodiment 7 | 22 | 870 | 0 | 0.32 | 0.42 | 32 | 37 | 23 | 78 |
| Embodiment 8 | 53 | 330 | 1 | 0.27 | 0.59 | 35 | 35 | 42 | 78 |
| Embodiment 9 | 52 | 315 | 1 | 0.26 | 0.56 | 30 | 36 | 43 | 75 |
| Comparative example 1 | ＞500 | ||||||||
| Comparative example 2 | 119 | 675 | 1 | 0.32 | 0.52 | - | 37 | 8 | 75 |
| Comparative example 3 | 60 | 110 | 62 | 0.4 | 0.97 | - | 36 | 25 | 12 |
| Comparative example 4 | 100 | 260 | 32 | 0.38 | 0.95 | - | 37 | 12 | 25 |
| Comparative example 5 | ＞500 |
In addition, the high water absorbency polymer that obtains with this manufacture method is that median size is big, size distribution is also narrow, loose density is high and the high water absorbency polymer of high absorption speed.
In addition, the high water absorbency polymer that obtains with the present invention is that primary particle is melting, incorporate granulated polymer.Even do not return primary particle after the suction of this polymkeric substance yet, keep granular shape, thereby show high gel sets.
The effect of invention
According to the present invention, when adopting via Inverse-Phase Suspension Polymerization to make high water absorbency polymer, use specific phosphoric acid salt surfactant, recycling dropping liquid polymerization is carried out polymerization, thus can be with utmost point simple operations and make at low cost the high water absorbency polymer with the above-mentioned speciality that did not in the past have. And such high water absorbency polymer is applicable to for example diaper made of paper and sanitary napkin, soil water-loss reducer.
The simple declaration of accompanying drawing
Fig. 1 is the sketch chart of the high water absorbency polymer (botryoidalis high water absorbency polymer) that obtains with the present invention of expression.
Fig. 2 is the sketch chart of the high water absorbency polymer (rock-like high water absorbency polymer) that obtains with the present invention of expression.
Fig. 3 is the sketch chart of the high water absorbency polymer (grain of rice shape high water absorbency polymer) that obtains with the present invention of expression.
Fig. 4 is the sketch chart that is illustrated in equipment therefor in the absorption speed of measuring high water absorbency polymer.
The explanation of symbol
1 high water absorbency polymer (1g)
2 have the supporting plate of aperture
3 non-woven fabrics
4 0.9% salt solutions
5 drop-burettes
6 rubber bolt
7,8 valves
9 gas inlets
Claims (4)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP118853/97 | 1997-04-22 | ||
| JP118853/1997 | 1997-04-22 | ||
| JP11885397 | 1997-04-22 |
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| Publication Number | Publication Date |
|---|---|
| CN1197804A CN1197804A (en) | 1998-11-04 |
| CN1106410C true CN1106410C (en) | 2003-04-23 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN98109296A Expired - Fee Related CN1106410C (en) | 1997-04-22 | 1998-04-22 | High water absorbency polymer and its preparation |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5998553A (en) |
| EP (1) | EP0874002B2 (en) |
| CN (1) | CN1106410C (en) |
| DE (1) | DE69825809T3 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6562879B1 (en) | 1999-02-15 | 2003-05-13 | Nippon Shokubai Co., Ltd. | Water-absorbent resin powder and its production process and use |
| DE60016326T2 (en) * | 1999-07-26 | 2005-11-24 | Nippon Shokubai Co., Ltd. | Water-absorbent composition and its use |
| CN100336563C (en) * | 2002-10-24 | 2007-09-12 | 大日本油墨化学工业株式会社 | Absorbent material and absorbent article |
| US20040204554A1 (en) * | 2003-04-09 | 2004-10-14 | Ko Young Chan | Process for making a multifunctional superabsorbent polymer |
| EP1677845B2 (en) | 2003-09-19 | 2016-06-22 | Nippon Shokubai Co., Ltd. | Water absorbent and producing method of same |
| SG155191A1 (en) * | 2004-08-06 | 2009-09-30 | Nippon Catalytic Chem Ind | Particulate water-absorbing agent with water-absorbing resin as main component, method for production of the same, and absorbing article |
| CN1314363C (en) * | 2005-04-27 | 2007-05-09 | 邵建国 | Throat-protecting tea and preparation method thereof |
| TWI383008B (en) * | 2005-08-17 | 2013-01-21 | Nippon Catalytic Chem Ind | Production method of water-absorbent resin, water-absorbent resin, and usage of water-absorbent resin |
| EP1997877B1 (en) | 2006-03-17 | 2014-03-05 | Sanyo Chemical Industries, Ltd. | Cell culture substrate |
| EP2112172B2 (en) * | 2007-01-24 | 2018-10-17 | Nippon Shokubai Co., Ltd. | Particulate water-absorbent polymer and process for production thereof |
| MX2010008990A (en) * | 2008-03-31 | 2010-09-10 | Sekisui Chemical Co Ltd | Intermediate film for laminated glass, laminated glass, and zinc oxide microparticle dispersion. |
| CN101977864B (en) * | 2008-03-31 | 2014-02-19 | 积水化学工业株式会社 | Intermediate film for laminated glass, laminated glass, and zinc oxide microparticle dispersion |
| US20100063186A1 (en) * | 2008-09-11 | 2010-03-11 | Sanford, L.P. | Washable ink compositions and writing instruments comprising same |
| AU2010323629A1 (en) * | 2009-11-27 | 2012-07-19 | Sumitomo Seika Chemicals Co., Ltd. | Process for production of water-absorbing resin particles, water-absorbing resin particles, water-stopping material, and absorbent article |
| WO2016088848A1 (en) * | 2014-12-05 | 2016-06-09 | 株式会社日本触媒 | Method for manufacturing super absorbent polymer |
| US20170022314A1 (en) * | 2015-07-24 | 2017-01-26 | Weyerhaeuser Nr Company | Grafted crosslinked cellulose |
| WO2017150108A1 (en) * | 2016-03-02 | 2017-09-08 | 住友精化株式会社 | Process for producing water-absorbing resin particles |
| US10988558B2 (en) * | 2016-11-08 | 2021-04-27 | DDP Specialty Electronic Materials US, Inc. | Controlled particle size distribution |
| CN110358117B (en) * | 2019-07-18 | 2022-08-12 | 台湾塑胶工业股份有限公司 | Water-absorbent resin composition, water-absorbent resin and method for producing the same |
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|---|---|---|---|---|
| EP0349240A2 (en) * | 1988-06-28 | 1990-01-03 | Nippon Shokubai Co., Ltd. | Water-absorbent resin and production process |
| EP0594009A2 (en) * | 1992-10-23 | 1994-04-27 | Kao Corporation | Process for producing polymer particles with irregular shape |
| EP0695762A1 (en) * | 1993-03-01 | 1996-02-07 | Kao Corporation | Method of manufacturing polymer particles of indeterminate form |
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| JPS60258213A (en) * | 1984-06-05 | 1985-12-20 | Mitsubishi Rayon Co Ltd | Manufacture of synthetic resin molded article with highly scratch-resistant surface |
| JPH03200840A (en) * | 1989-12-28 | 1991-09-02 | Nitto Chem Ind Co Ltd | W/o emulsion of cationic polymer |
| JP2917418B2 (en) * | 1990-05-31 | 1999-07-12 | 三菱化学株式会社 | Method for producing superabsorbent polymer |
| JP3005124B2 (en) † | 1992-09-10 | 2000-01-31 | 花王株式会社 | Method for producing amorphous polymer particles |
-
1998
- 1998-04-22 DE DE69825809T patent/DE69825809T3/en not_active Expired - Lifetime
- 1998-04-22 EP EP98107304A patent/EP0874002B2/en not_active Expired - Lifetime
- 1998-04-22 US US09/064,167 patent/US5998553A/en not_active Expired - Lifetime
- 1998-04-22 CN CN98109296A patent/CN1106410C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0349240A2 (en) * | 1988-06-28 | 1990-01-03 | Nippon Shokubai Co., Ltd. | Water-absorbent resin and production process |
| EP0594009A2 (en) * | 1992-10-23 | 1994-04-27 | Kao Corporation | Process for producing polymer particles with irregular shape |
| EP0695762A1 (en) * | 1993-03-01 | 1996-02-07 | Kao Corporation | Method of manufacturing polymer particles of indeterminate form |
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| Publication number | Publication date |
|---|---|
| EP0874002A3 (en) | 1998-11-04 |
| DE69825809T2 (en) | 2005-09-01 |
| EP0874002B2 (en) | 2008-08-27 |
| CN1197804A (en) | 1998-11-04 |
| DE69825809T3 (en) | 2009-04-16 |
| EP0874002A2 (en) | 1998-10-28 |
| US5998553A (en) | 1999-12-07 |
| EP0874002B1 (en) | 2004-08-25 |
| DE69825809D1 (en) | 2004-09-30 |
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